CN100565820C - Silicon wafer and manufacture method thereof - Google Patents

Silicon wafer and manufacture method thereof Download PDF

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CN100565820C
CN100565820C CNB2005800502295A CN200580050229A CN100565820C CN 100565820 C CN100565820 C CN 100565820C CN B2005800502295 A CNB2005800502295 A CN B2005800502295A CN 200580050229 A CN200580050229 A CN 200580050229A CN 100565820 C CN100565820 C CN 100565820C
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heat treatment
wafer
hydrogen
silicon
gas
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CN101238557A (en
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杉村涉
小野敏昭
宝来正隆
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Sumco Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/322—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to modify their internal properties, e.g. to produce internal imperfections
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/322—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to modify their internal properties, e.g. to produce internal imperfections
    • H01L21/3221—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to modify their internal properties, e.g. to produce internal imperfections of silicon bodies, e.g. for gettering
    • H01L21/3225—Thermally inducing defects using oxygen present in the silicon body for intrinsic gettering
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements
    • C30B29/06—Silicon
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
    • C30B33/02—Heat treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/324—Thermal treatment for modifying the properties of semiconductor bodies, e.g. annealing, sintering

Abstract

In the inert environments gas of the gas of the material that contains hydrogen atoms, by CZ method growing silicon single crystal.The wafer that silicon single crystal by growth obtains is implemented high-temperature heat treatment in non-oxidizing atmosphere gas, under 1000 ℃～1300 ℃.At this moment, before high temperature heat treatment step, implement Low Temperature Heat Treatment being lower than under the temperature of this temperature.

Description

Silicon wafer and manufacture method thereof
Technical field
The present invention relates to silicon wafer and manufacture method thereof, particularly relate to the manufacture method of the silicon wafer that the silicon single crystal ingot by Czochralski method (Czochralski method) preparation is obtained.The present invention relates to suppress the suitable technique used when slip dislocation is improved the intensity of wafer.
The application requires the priority of the application Japanese Patent Application submitted on July 27th, 2005 2005-217647 number, quotes its content at this.
Background technology
As the silicon single crystal wafer of the substrate of semiconductor device etc., by with silicon single crystal ingot, heat-treat or mirror finish waits and makes.As the preparation method of silicon single crystal ingot, for example can enumerate Czochralski method (CZ method).The CZ method is widely used in the preparation of silicon single crystal ingot owing to the bigbore single crystal rod that is easy to get, easily defective is controlled etc.
When being equipped with silicon single crystal by the CZ legal system, owing to use quartz crucible to carry out crystalline growth, the oxygen that contains hypersaturated state in the crystallization, this oxygen forms hot alms giver (TD) in the circuit of device forms the heat treatment process etc. of step, so the big problem that exists the resistivity of wafer to change astatically when the device manufacturing.
Under the situation of the conventional low resistance wafer that is added with dopant, the influence of the resistivity of hot donor pair wafer is slight, does not have problems in practical operation.But under the situation of the limited high resistance wafer of dopant, resistivity swashs and to subtract if the n type is then along with hot alms giver's increase.Though if the p type is then along with hot alms giver's increase, initial resistivity increase sharply, if hot alms giver further continues to increase, the p type is converted to the n type, resistivity is sharp subtracts.
Usually, to silicon wafer, because the resistivity that hot alms giver caused changes, implement the alms giver and eliminate (donor killer in order to prevent; DK) handle.For in the silicon wafer of hydrogen annealing, argon annealing, similarly, before The high temperature anneal, implement the alms giver and eliminate processing in order to suppress the resistivity change.Hot alms giver also is the factor that promotes that the oxygen precipitate forms except the factor for the resistivity change.
In the silicon single crystal that forms by the crystal pulling of CZ method, oversaturated oxygen enters between the lattice.Oversaturated oxygen becomes the reason of bringing out the tiny flaw that is called as BMD (BulkMico Defect) in the annealing in process of wafer process step etc.When forming semiconductor device on silicon single crystal wafer, requiring does not have crystal defect in device formation zone.If have crystal defect forming on the surface of circuit, then become the reason that causes circuit damage etc. by this defect part.
On the other hand, BMD has the effect that metal impurities to the reason that becomes crystal defect etc. carry out gettering.Therefore, in the DZ-IG method,, bring out BMD in the inside of silicon wafer, form IG (intrinsic gettering (Intrinsic Gettering)) layer by carrying out the annealing of silicon wafer.By the IG layer impurity is carried out gettering, on the surface of silicon wafer, form few DZ (DenudedZone) layer of crystal defect thus.
The DZ layer is integral in device forms.But if the silicon wafer that is formed with the DZ layer is annealed, then produce dislocation defects (Slip) and expansion on the DZ layer, the intensity of silicon wafer reduces.Particularly if wafer by the state of supports such as heat treatment mouth (Hot handle ボ one ト) under, the slip dislocation then of annealing might expand from the supported part of the back side periphery of wafer.If the intensity of silicon wafer reduces damage or the destruction that then easily produces wafer in step thereafter.Therefore, require silicon wafer with DZ layer, strength characteristics excellence.For fear of the problems referred to above, as described in TOHKEMY 2002-134521 communique, known technology of removing the wafer top layer, but owing to the increase of number of steps, the increase of slice thickness etc., can not avoid the increase of manufacturing cost.
Form oxidation and bring out stacking fault (Oxidation Induced Stacking Fault, the tiny flaw of the oxygen precipitate of nuclear OSF), particle (the Crystal Originated Particle that causes by crystallization, COP), (Interstitial-type Large Dislocation LD) causes that when making semiconductor device yield reduces to intrusion type dislocation.Therefore, it is important making the few wafer of such defective.The flawless silicon wafer of no OSF, COP and LD is disclosed in the Japanese kokai publication hei 11-1393 communique.On the other hand, when making semiconductor device, sometimes must no OSF, COP and LD and silicon wafer with gettering ability.
Summary of the invention
But the flawless silicon wafer of above-mentioned no OSF, COP and LD in the heat treatment of device manufacturing step, may not be separated out at the inner oxygen that produces of wafer.Therefore, in the heat treatment in the DZ-IG method, the slippage expansion, the result can not get rid of the possibility that die strength reduces.
Further, even when not using above-mentioned flawless silicon wafer, in the heat treatment in the DZ-IG method, also expectation prevents the expansion of slip dislocation.
The present invention is in view of the above problems and proposes, and when the invention provides the high-temperature heat treatment of carrying out more than 1000 ℃ in DZ-IG method etc., by suppressing the slippage expansion, prevents silicon wafer and manufacture method thereof that die strength reduces.
The present application people studies intensively, found that, by in crystal pulling, in the inert environments gas of the gas of the material that contains hydrogen atoms, carry out the CZ crystalline growth, compare with the crystalline growth condition of not adding hydrogen, under the state of growth (as-grown), in body crystallization (バ ル ク Knot crystalline substance), formed highdensity hot alms giver (TD).
(with reference to Figure 13)
Hot alms giver for the factor of resistivity change, also be the factor that promotes that the oxygen precipitate forms.Therefore, passing through high annealing (Ar/H 2Annealing) eliminate hot alms giver and implement Low Temperature Heat Treatment before, can in body piece (バ Le Network), form highdensity small size oxygen and separate out nuclear.Small size oxygen is separated out nuclear plays a part to stop slippage in high-temperature heat treatment expansion.Having on the highdensity silicon wafer of separating out nuclear,, suppress the expansion of slip dislocation by in high-temperature annealing step, being formed at the precipitate on the dislocation line.
The manufacture method of the silicon wafer of the present invention that proposes based on above-mentioned discovery comprises:
In the inert environments gas of the gas of the material that contains hydrogen atoms, by the step of CZ method growing silicon single crystal,
Cut out the step of wafer by above-mentioned silicon single crystal,
In non-oxidizing atmosphere gas, under 1000 ℃～1300 ℃, above-mentioned wafer is implemented heat treated high temperature heat treatment step,
Before above-mentioned high temperature heat treatment step, be lower than under the temperature of above-mentioned heat treatment temperature, above-mentioned wafer is implemented heat treated Low Temperature Heat Treatment step.Thus, the problems referred to above are resolved.
The manufacture method of silicon wafer of the present invention comprises:
In the inert environments gas of the gas of the material that contains hydrogen atoms, by the step of CZ method growing silicon single crystal,
Cut out the step of wafer by above-mentioned silicon single crystal,
Above-mentioned wafer is implemented to be used to prevent that the alms giver of resistivity change from eliminating heat treated alms giver and eliminating heat treatment step,
Before above-mentioned alms giver eliminates heat treatment step, be lower than under the temperature of above-mentioned heat treatment temperature, above-mentioned wafer is implemented heat treated Low Temperature Heat Treatment step.Thus, the problems referred to above are resolved.
The scope of the treatment temperature of above-mentioned Low Temperature Heat Treatment step is 400 ℃～650 ℃, and more preferably heating rate is 0.2 ℃/min～2.0 ℃/min.
In the manufacture method of above-mentioned silicon wafer, above-mentioned heat treatment step can adopt gradient heat treatment (ラ Application ピ Application グ Hot processing).
Also can use by above-mentioned Low Temperature Heat Treatment step, making the difference in oxygen concentration between of above-mentioned high temperature heat treatment step front and back is 1.5 * 10 17Individual atom/cm 3More than the device or the method for (ASTM-F121 1979).
Hydrogen concentration in the inert environments gas in the above-mentioned crystal growth, (10～100torr) are set in 0.1%～20% scope with respect to furnace pressure 1.3～13.3kPa.
Among the present invention, preferably making the oxygen precipitate density after the above-mentioned high-temperature heat treatment is 1.0 * 10 10Individual/cm 3More than.
Silicon wafer of the present invention can be by above-mentioned any described manufacture method manufacturing.
The manufacture method of silicon wafer of the present invention comprises: in the inert environments gas of the gas of the material that contains hydrogen atoms, by the step of CZ method growing silicon single crystal; Cut out the step of wafer by above-mentioned silicon single crystal; The high temperature heat treatment step of carrying out in non-oxidizing atmosphere gas, under 1000 ℃～1300 ℃ or be used to prevents that the alms giver of resistivity change from eliminating heat treatment step; Before above-mentioned high temperature heat treatment step or above-mentioned alms giver eliminate heat treatment, be lower than the Low Temperature Heat Treatment step of carrying out under the temperature of above-mentioned heat treatment temperature.If in the inert environments gas of the gas of the material that contains hydrogen atoms,, then under the state of growth, in body piece monocrystalline, form highdensity hot alms giver (TD) by CZ method growing silicon single crystal.By the wafer that is obtained by this single-crystal wafer being implemented above-mentioned Low Temperature Heat Treatment step, in the body piece, form highdensity undersized oxygen and separate out nuclear, separate out nuclear by the highdensity oxygen of this small size, can be suppressed in the high-temperature heat treatment or the alms giver eliminates the slippage expansion that produces in the heat treatment.
The highdensity hot alms giver (TD) who forms under growth conditions by the gradient heat treatment under the low temperature, forms the oxygen precipitate.Handle by the hydrogen doping wafer that contains highdensity hot alms giver is implemented low temperature gradients, can in the body piece, form highdensity little oxygen precipitate.In order to suppress the slippage expansion in the heat treatment, under the temperature (more than 900 ℃) of the beginning expansion of staggering on the throne, it is important separating out the oxygen precipitate on the dislocation line of slippage propagation direction.If adopt low temperature gradients to handle (low temperature ラ Application ピ Application グ processing), then contain small size, highdensity precipitate in the body piece by making, can promote to separate out, thereby suppress the slippage expansion.
Usually, for silicon wafer, implement the alms giver for the resistivity change that prevents to cause and eliminate (donor killer, DK) processing owing to hot alms giver.For supplying, similarly, before The high temperature anneal, implement the alms giver down and eliminate processing about 0.5～2 hour at 600 ℃～700 ℃ in order to suppress the resistivity change in the silicon wafer of hydrogen annealing, argon annealing.Therefore, when implementing gradient heat treatment, preferably (being in the state that has sufficient hot alms giver) carries out before the alms giver eliminates processing.
In order to suppress the slippage expansion in the high temperature heat treatment step, must in body agllutination crystalline substance, form highdensity undersized oxygen and separate out nuclear.Among the present invention, the treatment temperature by making above-mentioned Low Temperature Heat Treatment step is 0.2 ℃/min～2.0 ℃/min, 0.3 ℃/min～1.0 ℃/min more preferably at 400 ℃～650 ℃ temperature range and heating rate, can form preferred oxygen and separate out nuclear.
When handling by vertical heater etc., owing to derive from the pollutant of high temperature furnace wall, it is bigger to produce contamination of heavy in heat treatment.Carry out above-mentioned heat treatment step by gradient heat treatment, reduce possibility of pollution thus, exactly heating rate is controlled, can make the temperature conditions severization.The formation state of thus, can be exactly oxygen being separated out nuclear is controlled, is obtained having the wafer that desired oxygen is separated out nuclear.
By implementing above-mentioned Low Temperature Heat Treatment step, can make the difference in oxygen concentration between of above-mentioned high temperature heat treatment step front and back is 1.5 * 10 17Individual atom/cm 3More than (ASTM-F121 1979) reduce oxygen concentration.The formation state of thus, can be exactly oxygen being separated out nuclear is controlled, is obtained having the wafer that desired oxygen is separated out nuclear.
Hydrogen concentration in the inert environments gas during for crystal growth is that 1.3～13.3kPa (under 10～100torr) the condition, can be set in 0.1%～20% scope at furnace pressure.In the wafer that cuts out by the monocrystalline of under this environmental gas, growing, keep the state that desired oxygen is separated out nuclear, form sufficient oxygen and separate out nuclear in case on-slip moves expansion by above-mentioned Low Temperature Heat Treatment.For the hydrogen concentration in the inert environments gas, be that 4.0～9.33kPa (under 30～70torr) the condition, can be set in 0.3%～10% scope at furnace pressure.
Among the present invention, be 1.0 * 10 by making the oxygen precipitate density after the above-mentioned high-temperature heat treatment 10Individual/cm 3More than, can fully suppress the slippage expansion in the high-temperature heat treatment.
Wherein, above-mentioned oxygen precipitate be preferably dimensioned to be about 80～200nm, the size about 100nm more preferably.
Wherein, among Fig. 1 and Fig. 2, represent that with the longitudinal axis oxygen is separated out cuclear density, transverse axis is represented size.Among the figure, symbol BB is the boundary line of critical BMD size residual under the temperature of expression more than 900 ℃.
When not implementing low temperature gradients heat treatment (Low Temperature Heat Treatment), as shown in Figure 1, in the preceding body piece of high annealing (argon annealing), the density of the BMD more than 900 ℃ the critical BMD size on boundary B B right side is 1.0 * 10 9Individual/cm 3About (1.0 * 10 9Ge/cm 3Platform).On the other hand, when implementing low temperature gradients heat treatment, owing to produce the growth of separating out nuclear when separating out the formation of nuclear with oxygen, as shown in Figure 2, the bmd density more than 900 ℃ the critical BMD size on boundary B B right side is 1.0 * 10 10Individual/cm 3About (1.0 * 10 10Ge/cm 3Platform).
Thus, when carrying out the high annealing (argon annealing) more than 1200 ℃, in having implemented the heat treated wafer of low temperature gradients, guaranteed that bmd density is 1.0 * 10 10Individual/cm 3More than, by highdensity BMD, suppressed the slippage expansion in the high-temperature heat treatment.
By experiment in advance, consider that the combustion boat (ボ one ト) of argon annealing steps drops into temperature, gradient speed, obtain the result who equates with bmd density more than 900 ℃ the critical BMD size by the residual bmd density of high annealing (argon annealing).Therefore, the border is set in 900 ℃.
Wafer of the present invention can be by above-mentioned any described manufacture method manufacturing.
The inventor is conceived to carry out with hydrogeneous environmental gas the technology of crystal pulling and studies, and the result reaches following 2 conclusions.
The 1st, at the stove that uses thermal field structure, the temperature gradient Gc that is controlled to nucleus of crystal portion equates with the temperature gradient Ge of crystallization peripheral part or the former is bigger, when slowly reducing pulling rate under the situation of growing single-crystal, what the OSF in the longitudinal section of monocrystalline produced the zone being shaped as below projection, terminal more flat U word shape.When observing on the crystallization cross section, when pulling rate was fast, OSF produced zone shape in the form of a ring, and side is observed the zone that produces COP (being also referred to as the infrared diffusion volume defect) within it.The OSF of ring-type produces the zone, along with reducing in nucleus of crystal portion of pulling rate.Dislocation group generation zone then appears if further reduce pulling rate.
Under above-mentioned crystal pulling condition, if sneak into the hydrogen of trace in the inert gas in importing crystal pulling furnace, then realize the pulling rate expanded range of zero defectization, in the defect distribution of crystallization longitudinal section, area free from defect upwards enlarges at crystal axis.The paired observation of B '-C ' of the B-C of Fig. 3 that this effect can be when undoping hydrogen and the Fig. 4 during doped with hydrogen is arrived.
The pulling rate condition of the B-C scope among Fig. 3 is for OSF produces near the crystal pulling condition of the zone critical speed that nucleus of crystal portion disappears.By under this velocity conditions, carrying out crystal pulling, can make crystallization Zone Full zero defectization radially.
By adding the expansion that hydrogen makes the pulling rate scope of zero defectization, be to realize by the reduction that OSF produces the rising of the critical speed Vo that the zone disappears in nucleus of crystal portion and produces the critical speed Vd of dislocation group.Pulling rate scope the B '-C ' of realization zero defectization shown in Figure 4, the B-C of the Fig. 3 when not adding hydrogen compares, and is the top of the B among Fig. 3 and is that the below of the C among Fig. 3 enlarges to low speed one side to a side at a high speed.This phenomenon can be passed through the following explanation of Fig. 5.
Fig. 5 describes with regard to the degree of influence of defect distribution to the relation of pulling rate and OSF ring diameter.Among the figure, dotted line is the temperature gradient Gc of the nucleus of crystal portion situation littler than the temperature gradient Ge of crystallization peripheral part.At this moment, on one side the OSF that slowly reduces in the longitudinal section of the monocrystalline that pulling rate grows on one side produce the being shaped as V font that protrude the below in zone.At this moment, along with the reduction of pulling rate, the OSF ring diameter slowly dwindles, and bringing together at critical speed Vo is 0.
Thinner solid line is under the condition of not adding hydrogen, the situation that temperature gradient Ge equates or the former is bigger of the temperature gradient Gc of nucleus of crystal portion and crystallization peripheral part.At this moment, on one side the OSF that slowly reduces in the longitudinal section of the monocrystalline that pulling rate grows on one side produce the shape U fontization in zone.At this moment, pulling rate that the OSF ring diameter begins to dwindle reduces, and produce from this commencing speed and sharply dwindle, be 0 bringing together with the roughly the same pulling rate Vo of the situation of dotted line.That is, the minimizing gradient variable of the constant and ring diameter of critical speed Vo is anxious.Thus, near critical speed Vo, be grown in the flawless monocrystalline that crystallization does not radially exist dislocation group and COP on the Zone Full.But because critical speed Vo does not rise, must make pulling rate is low speed.
In addition, thicker solid line is to add in inert gas environment gas under the condition of hydrogen, the situation that temperature gradient Ge equates or the former is bigger of the temperature gradient Gc of nucleus of crystal portion and crystallization peripheral part.At this moment, on one side slowly reduce the shape that OSG in the longitudinal section of the monocrystalline that pulling rate grows produces the zone on one side and become the U font.At this moment, compare with thinner solid line, the minimizing gradient of ring diameter still rises to Vo ' for anxious gradient critical speed from Vo.If solid line that will be thinner then corresponds essentially to thicker solid line to a side is parallel mobile at a high speed.
As mentioned above, add hydrogen by combination in the growth of no primary (Grown-in) defective crystallization, increased the critical speed that ring OSF zone disappears in nucleus of crystal portion, can be grown under the growth conditions monocrystalline that does not radially have the no primary defective of dislocation group and COP in crystallization in the Zone Full by speed ratio fast in the past crystal pulling.Further, because by adding hydrogen, the pulling rate Vd that produces the upper limit of dislocation group is reduced to Vd ', realize that the pulling rate scope of zero defectization expands B '-C ' to from B-C.Thereby can stably grow the zero defect crystallization, the manufacturing yield that does not have primary defective crystallization significantly improves.
Add hydrogen by combination, realize the reason of the pulling rate expanded range of no primary defectiveization, the reason that the critical speed Vo that promptly encircles OSF increases, the critical speed Vd of generation dislocation group reduces thinks as described below.
In 1300～1390 ℃ high temperature hydrogen to silicon wafer heat-treat, during chilling, silicon and H-H reaction form (the positive will in pool, end of silicon-hydrogen complex between hole-hydrogen or lattice between hole or lattice, on June 3rd, 1999, the 110th time text P11 of research association of Applied Physics association crystallization engineering branch meeting).Therefore, when in containing the inert environments gas of hydrogen, growing the CZ crystallization, the high-temperature portion that is higher than the temperature that primary defective such as COP (about 1100 ℃) or dislocation group (about 1000 ℃) forms in the crystallization cooling procedure, in the silicon crystallization, silicon and H-H reaction between the hole of excessive existence or lattice form between hole-hydrogen or lattice complexs such as silicon-hydrogen.Owing to, reduced the concentration of silicon between hole and lattice, suppressed the cohesion of silicon between hole or lattice, no COP and the dislocation of can growing group and the little CZ crystallization of size by the formation of complex.
But known: in hydrogeneous inert environments gas under the fully big hole superiority condition of V/G, during growth CZ crystallization, then can form the huge cavity (thinking the agglomerate in hole) (E.Lino, K.Takano, M.Kimura, H.Yamagishi:Material Science and EngineeringB36 (1996) 146-149 and T.H.Wang, T.F.Ciszk, and T.Schuyler:J.Cryst.Growth109 (1991) 155-161) that is called as hydrogen defect and is of a size of several μ m～several 10 μ m if increase hydrogen concentration.Under silicon superiority condition between the fully little lattice of V/G, can form the hydrogen defect dislocation of the agglomerate of silicon between lattice (think to) (Y.Sugit:Jpn.J.Appl.Phys 4 (1965) p962) of silicon type between lattice.
Therefore, even pulling rate is not reduced to below the critical speed that produces ring OSF zone, when in containing the environmental gas of sufficient hydrogen, using the CZ farad brilliant, also can suppress the generation of COP.Even when the low speed crystal pulling, also can suppress the generation of dislocation group.
Near the relation of the ratio V/G of the temperature gradient G of crystallization one side the concentration C v of silicon and Ci and pulling rate V and the solid liquid interface between the hole under the temperature and lattice more than 1100 of nucleus of crystal portion ℃ when Fig. 6 is the CZ crystalline growth, the generation of COP when being present in the crystallization to hydrogen and dislocation group suppresses effect and describes.Use this figure that the reason of the generation of inhibition COP and dislocation group is described.Wherein, Vo, Vc and Vd are respectively in a nucleus of crystal portion or a part radially and begin to generate the critical speed that ring OSP zone, COP zone and dislocation are rolled into a ball, and Cv-OSF, Cv-COP and Ci-disk represent the critical point defect density that OSF ring zone, COP and dislocation group generate respectively.
Crystallization for the no primary defective of can growing, use contains and is designed to the CZ stove of thermal field that on crystallization direction V/G satisfies the relation of Gc 〉=Ge, during the growth crystallization, if make pulling rate greater than Vc (situation of [H2]=0 among Fig. 6), the point defect kind (some Qian Xian Seed) that then produces the hole advantage usually is COP.But in the environmental gas of the gas of the material that contains hydrogen atoms during growth CZ crystallization (situation of H1, H2 among Fig. 6), because the hole forms complex with hydrogen, the concentration reduction of free hole.The concentration of this free hole reduces the hydrogen concentration that depends in the crystallization, and the reduction of the big more then hole concentration of hydrogen concentration is many more.Therefore, when having hydrogen, the pulling rate Vo that generates the OSF ring is as Vo ', Vo " move to a lateral deviation at a high speed, the pulling rate Vc that generates COP is also as Vc ', Vc " move to high speed one lateral deviation.
On the other hand, if pulling rate is less than Vd (situation of [H2]=0 among Fig. 6), silicon is the point defect kind of advantage between lattice, and the concentration of silicon is Ci＞Ci-disl between lattice, and the form with 2 defectives of silicon between lattice produces dislocation group usually.But when in the environmental gas of the gas of the material that contains hydrogen atoms, growing (situation of [H2]=H1 or H2 among Fig. 6), because silicon forms complex with hydrogen between lattice, the concentration of silicon reduction between lattice freely.Therefore, the pulling rate Vd of product dislocation group, consistent with critical concentration Ci-disl the more Vd ' or the Vd of low speed one side " skew.
Shown in [the H2]=H1 and H2 of Fig. 6, when hydrogen concentration is relatively low,, then, can not suppress the generation of COP fully because hole concentration is bigger than the critical concentration Cv-COP that generates COP if V/G fully increases.But owing to compare when not having hydrogen, hole concentration reduces, and the size of COP reduces.
At critical speed Vo ' or the Vo that OSF ring produces " the critical speed Vd ' or the Vd of following and dislocation group generation " more than the scope of pulling rate in, because the concentration of silicon is enough low between hole and lattice, do not produce COP and dislocation group, and do not produce hydrogen defect that huge cavity is a cavity type or dislocation yet being the hydrogen defect of silicon type between lattice.Further, compare when not adding hydrogen, since the significantly expansion of the scope (margin) of the pulling rate of no primary defective, the zero defect crystallization of can more stably growing with high yield.
Though the critical V/G condition that disappears is compared, V/G is bigger encircling with OSF, but approach under the situation of critical condition, though ring OSF does not disappear in nucleus of crystal portion, COP produces in the territory, lateral areas within it, its size is owing to reduce and reduce by interpolation hydrogen, hole concentration.In addition, under this situation,, can not produce huge cavity because hole concentration is fully low.
Hydrogen concentration in the above-mentioned inert environments gas is that 1.3～13.3kPa (under 10～100torr) the condition, can be set in 0.1%～20%, more preferably 3%～10% scope at furnace pressure.Furnace pressure is more than the 1.3kPa (10torr), and (10～100torr), more preferably 4.0～9.33kPa (30～70torr) to be preferably 1.3～13.3kPa.If the hydrogen concentration that the dividing potential drop of hydrogen reduces in the then melt and crystallization reduces.In order to prevent these problems, the lower limit of furnace pressure is stipulated.If reduce the Ar flow velocity, then be difficult to carrying out exhaust by the carbon of the carbon heater or carbon part (the カ one ボ Application パ one Star) degassing, the reactant gas such as SiO that evaporate by liquation.Thus, concentration of carbon increases, and about 1100 ℃ or the more part cohesion of low temperature on the liquation top of SiO in stove produce ash thus, fall in the liquation, cause that crystallization produces dislocation.In order to prevent these problems, the upper limit of furnace pressure is stipulated.
Hydrogen concentration in the silicon single crystal during to growth in containing the inert environments gas of hydrogen can be controlled by the hydrogen dividing potential drop in the environmental gas.Hydrogen in the environmental gas is dissolved in and forms stable (balance) state in the melted silicon, by the concentration segregation concentration in liquid phase and the solid phase is distributed during crystallization and freezing.Thereby in crystallization, import hydrogen.
Hydrogen concentration in the liquation, the hydrogen dividing potential drop that is depended on as can be known in the gas phase by Henry's law decides, and is expressed as:
P H2＝kC LH2
Wherein, P H2Be hydrogen dividing potential drop, the C in the environmental gas LH2For the hydrogen concentration in the melted silicon, k are coefficient between the two.
On the other hand, the hydrogen concentration in the crystallization is expressed as by the relation decision of hydrogen concentration in the liquation and segregation:
C SH2＝k’C LH2＝(k’/k)P H2
Wherein, C SH2It for the hydrogen concentration in the crystallization, k ' segregation coefficient between the melted silicon-crystallization of hydrogen.
Shown in following formula, by the hydrogen dividing potential drop in the environmental gas is controlled, can crystallization axially on desired concentration the hydrogen concentration in the crystallization after just solidifying is controlled consistently.
For silicon wafer of the present invention, the crystallization of also can growing in the inert environments gas of the gas of the material that contains hydrogen atoms is formed in the silicon wafer that only contains silicon dominant area between lattice (PI zone) in the Zone Full of wafer.At this moment, wafer can be kept the uniformity in the wafer owing to do not contain the PV zone.
Wherein, the uniformity of wafer refers to the density of oxygen precipitate and the uniformity of size and DZ width etc.At this moment, the temperature and time during with oxygen concentration and heat treatment etc. is a parameter, and can be set at respectively: oxygen concentration is 10～20 * 10 in the mensuration of carrying out according to ASTM-F1211979 17Individual atom/cm 3, more preferably 12～18 * 10 17Individual atom/cm 3, heat treatment temperature is 450 ℃～1400 ℃, more preferably 1100 ℃～1250 ℃, the time is more than 0 second.Thus, can obtain density and size and DZ width significantly uniform excellent wafer in the face of wafer of oxygen precipitate.
At this moment, the oxygen concentration in the monocrystalline (Oi) can be set in 10～20 * 10 17Individual atom/cm 3(ASTM-F1211979) high scope is carried out RTA and is handled.At this moment, be not used for making the high temperature long heat treatment of oxygen forming DZ layer process to foreign side's diffusion, can obtain guaranteeing fully the gettering ability the oxygen precipitate density, size and can make the device active region fully flawless enough DZ width can guarantee uniform excellent wafer.In addition, the oxygen concentration in the monocrystalline (Oi) can be set in 10 * 10 17Individual atom/cm 3Below in the low scope of (ASTM-F121 1979).At this moment,, also can suppress the oxygen precipitate in the generation of device in the active region, thereby can reduce or eliminate this oxygen precipitate even device is heat-treated, thus the characteristic that can the get auto levelizer excellent wafer of variation not.
Among the present invention, as method of growing silicon single crystal, by in the inert environments gas of the gas of the material that contains hydrogen atoms, silicon single crystal being carried out crystal pulling, can enlarge the scope of PI zone pulling rate that can crystal pulling becomes crystallization radially not contain COP and dislocation group in the Zone Full and contain the monocrystalline of silicon dominant area between lattice (PI zone).Therefore, can make monocrystalline vertical tube part (straight metastomium) be silicon dominant area (PI zone) between the lattice that does not contain dislocation group.In the past, when carrying out crystal pulling, PI zone pulling rate must be set in the extremely narrow scope there not being primary defective monocrystalline.Among the present invention, by enlarging the scope of PI zone pulling rate, can be extremely easily and with faster than the monocrystalline of the no primary defective of speed growth of pulling rate in the past.
Wherein, for the scope of PI zone pulling rate, when in the hydrogen environmental gas and in the inert environments gas of no hydrogen, comparing, compare with the state of invariableization of value of the axial-temperature gradient G in the above-mentioned crystallization after just having solidified.
Specifically, when in the hydrogen environmental gas, carrying out the monocrystalline crystal pulling, the PI zone pulling rate scope that can crystal pulling becomes the no primary defective monocrystalline that the no primary defect area (PI zone) by silicon type between lattice constitutes, become monocrystalline to compare with crystal pulling under the condition of no hydrogen, can be extended to more than 4 times or even 4.5 times scope as shown in Figure 7.
At this moment, also can reduce the generation zone of OSF ring.And the size of PV zone (the primary defect area of no cavity type) does not change because of adding hydrogen.
Among the present invention, as the pulling rate scope of the zone of the PI in the above-mentioned growing method, can increase crystal pulling and become the necessary pulling rate scope of no primary defect silicon monocrystalline.Therefore, can carry out crystal pulling with identical crystal pulling condition when a plurality of monocrystalline are carried out crystal pulling, can more easily set the monocrystalline that the pulling rate crystal pulling becomes no primary defective.Promptly, when repeatedly or simultaneously becoming the monocrystalline of no primary defective with a plurality of physical device crystal pullings with identical physical device, compared with the past, can simplify the crystal pulling condition enactment, can obtain can crystal pulling becoming the pulling rate scope of no primary defective monocrystalline, the monocrystalline that can crystal pulling one-tenth has desired quality.By this simplification, operating efficiency improves, silicon single crystal or significantly reduced by the manufacturing cost of the silicon wafer of this silicon single crystal manufacturing.
The material of employed hydrogen atoms is thermal decomposition can be in being dissolved in melted silicon the time, supplies with the material of hydrogen atom in melted silicon among the present invention.Import in the inert gas environment gas by material, can improve the hydrogen concentration in the melted silicon this hydrogen atoms.As the material of hydrogen atoms, for example, can use hydrogen, H 2The inorganic compound of hydrogen atoms such as O, HCl, silane gas, CH 4, C 2H 2Deng hydrocarbon, alcohol, the various materials of hydrogen atoms such as carboxylic acid.Material as hydrogen atoms preferably uses hydrogen.As inert gas, be preferably cheap Ar gas.Except Ar, can also use various rare gas simple substance or their mists such as He, Ne, Kr, Xe.
Among the present invention, the concentration of the hydrogenous material in the ambient containing hydrogen gas is represented with hydrogen conversion concentration.Wherein, with hydrogen conversion concentration represent be because, the decisions such as quantity of the hydrogen atom that the amount of the hydrogen atom that hydrogenous material thermal decomposition etc. obtains was contained originally by hydrogenous material.For example, 1 mole of H 2Contain 1 mole H among the O 2, and only contain 0.5 mole H among 1 mole of HCl 2Therefore, among the present invention, will with normal concentration in inert gas, import hydrogen and the ambient containing hydrogen gas that obtains as benchmark, preferably obtain becoming the concentration that the equal environmental gas of the environmental gas of benchmark decides hydrogenous material with this, this moment, the concentration of preferred hydrogenous material was represented with hydrogen conversion concentration.
That is, if the hypothesis hydrogenous material be dissolved in the melted silicon, in the melted silicon of high temperature thermal decomposition be converted to hydrogen atom then can adjust hydrogenous material addition so that the hydrogen conversion concentration in the environmental gas after the conversion in prescribed limit.
In the manufacture method of the present invention, in being present in ambient containing hydrogen gas in the inert gas, hydrogenous material forms silicon single crystal.The hydrogen atom that derives from hydrogenous material dissolves in the melted silicon, and further this hydrogen atom enters when silicon solidifies between the lattice of silicon.
The hydrogen addition is insufficient if then improve the effect of critical speed inadequately.When escape of air is in stove more at most as if the hydrogen addition, there is burning and even produces the danger of exploding.Therefore, the lower limit of hydrogen addition is preferably more than the 0.1 volume %, is preferably especially more than the 3 volume %.Less than 0.1% o'clock effect of no hydrogen almost.If hydrogen conversion concentration surpasses 50% (the hydrogen dividing potential drop is 6.75kPa) then because when oxygen leakage was in the CZ stove, blast etc. are dangerous to increase, not preferred on safety.It is then not preferred but the danger of burning increases if hydrogen conversion concentration surpasses 20% (the hydrogen dividing potential drop is 2.7kPa) owing to not producing blast.If hydrogen concentration be 20% with next owing to produce oxygen when leak waiting, even produce burning in stove, the pressure oscillation during burning is no more than 1 atmospheric pressure, does not have problems on safety.Thus, the upper limit of hydrogen addition is stipulated.The concentration of preferred hydrogenous material (hydrogen) is 0.1%～20%, and particularly preferred concentration is 3%～10%.
There is oxygen (O in the inert environments gas 2) time, concentration that the hydrogen molecule of gas converts and 2 times concentration difference of oxygen concentration are defined as the above concentration of 3 volume %.If concentration that the hydrogen molecule of the gas of hydrogen atoms converts and 2 times concentration difference of oxygen concentration then can not obtain the effect of the generation of primary defectives such as the inhibition COP that realizes by the hydrogen atom that enters in the silicon single crystal and dislocation group less than 3 volume %.
If the nitrogen as the impurity in the inert gas is high concentration, then silicon single crystal might have dislocation.(in 10～100Torr) the scope, preferred nitrogen concentration is below 20% to press 1.3～13.3kPa in common stove.
In the CZ stove during hydrogen supply, can be by commercially available hydrogen gas storage cylinder, hydrogen storage tank, filled the jar etc. of hydrogen bearing alloy that storage has hydrogen by special-purpose pipeline, supply in the crystal pulling furnace.
Use the temperature gradient Gc of nucleus of crystal portion to produce the common thermal field structure that the zone forms the V-shape of below point than ring OSF in the temperature gradient Ge longitudinal section little, the monocrystalline of growth when slowly reducing pulling rate of peripheral part, when near critical speed, carrying out crystal pulling, in other words, during Ge＞Gc, if hydrogen is added in combination, the effect by hydrogen then, begin to produce the critical speed Vo, the Vc that encircle OSF generation zone and COP in nucleus of crystal portion and increase, in the part of crystallization, begin to produce the critical speed Vd reduction of dislocation group.Therefore, though Ge＞Gc, both comparatively near the time, also might obtain not having the crystallization of not having primary defective fully of COP or dislocation group, but the scope of pulling rate if compare when satisfying Ge≤Gc, can not stably be made the crystallization of no primary defective.In addition, when the difference of Ge＞Gc and Ge and Gc is big, even add the velocity interval that hydrogen can not obtain not having primary defective.
The present invention finishes with the above-mentioned basis that is found to be.Silicon wafer of the present invention is to the wafer of the silicon single crystal by the growth of CZ method in the inert environments gas of the gas of the material that contains hydrogen atoms, implements the silicon wafer that heat treatment obtains by above-mentioned Low Temperature Heat Treatment step and elevated temperature heat step.
As high temperature heat treatment step, for example can use RTA (Rapid ThermalAnnealing).An example as the RTA condition can adopt from 1100 to 1350 ℃, more than 0 second, at Ar, He, contain NH 3Ar or the condition in the He environmental gas.At this moment, be not used for making the oxygen that forms DZ layer process high temperature long heat treatment down, can obtain to guarantee fully density, the size of oxygen precipitate of gettering ability and the excellent wafer that the complete flawless enough DZ width in device active region can be guaranteed equably to foreign side's diffusion.
At this moment, if the wafer of the no primary defective in the past that mixes for PV, PI or ring OSF zone carries out RTA same as described above and handles, then when crystalline growth, in the PV of hole advantage and the ring OSF zone, the density of oxygen precipitate and size are compared increase with the PI zone, in addition, the DZ narrowed width, further, because the oxidation processes on the device exists in the uneven problem of encircling generation defect distribution such as OSF region generating OSF.The no primary defect chip uniformly in wafer face in the only PI zone that obtains by the present invention has solved this problem.
According to the present invention, by growing silicon single crystal ingot in the inert gas environment of the gas of the material that contains hydrogen atoms, can obtain containing highdensity hot alms giver's silicon single crystal ingot, by the silicon wafer that is obtained by this silicon single crystal ingot is implemented low temperature gradients heat treatment, can in the body piece, form highdensity little oxygen precipitate.By so in the body piece, containing small size, highdensity precipitate, separating out in high-temperature heat treatment obtains promoting, under the temperature (more than 900 ℃) that begins to expand by the slip dislocation in heat treatment, on the dislocation line of the direction that slippage is expanded, separate out sufficient oxygen precipitate, can suppress the slippage expansion.
Description of drawings
[Fig. 1] is for to separate out the density of nuclear and the figure that distribution of sizes describes to the oxygen in the body piece before the high annealing.
[Fig. 2] separates out the density of nuclear and the figure that distribution of sizes describes for the oxygen in the body piece when implementing low temperature gradients heat treatment before high annealing.
[Fig. 3] is the defect map in the longitudinal section of the monocrystalline that reduces on one side slowly pulling rate and grow on one side, and the temperature gradient Gc of nucleus of crystal portion is described with the situation that temperature gradient Ge equates or the former is bigger of crystallization peripheral part.
[Fig. 4] while being the defect map that slowly reduces in the longitudinal section of the monocrystalline that pulling rate grows, and the temperature gradient Gc of nucleus of crystal portion is equated with the temperature gradient Ge of crystallization peripheral part or the former situation bigger and interpolation hydrogen describes.
[Fig. 5] is the figure of description defect distribution to the degree of influence of the relation of pulling rate and OSF ring diameter.
Near the relation of the ratio V/G of the temperature gradient G of crystallization one side the concentration C v of silicon and Ci and pulling rate V and the solid liquid interface between the hole under the temperature more than 1100 ℃ of nucleus of crystal portion and lattice when [Fig. 6] Fig. 6 is the CZ crystalline growth.
[Fig. 7] is the schematic diagram to describing by the variation of adding the pulling rate zone that hydrogen realizes.
[Fig. 8] is the longitudinal section of the CZ stove that is suitable for implementing the silicon single crystal preparation method in the present embodiment.
The chart that [Fig. 9] describes various generation of defects zone for the relation by V/G and hydrogen concentration is to describing the V/G zone expansion that produces defective by adding hydrogen.
The chart that [Figure 10] describes for the relation of crystallization position and obtaining not being had the pulling rate scope (margin) of primary defect area.
[Figure 11] is for to being used to carry out the board-like (Mei Leaf formula of Low Temperature Heat Treatment step) the schematic diagram that describes of gradient thermal treatment device.
[Figure 12] Figure 12 A, B, C are the crystallization cross-section photograph that is used to verify that the V word crystal pulling of the variation by adding each crystal region that hydrogen realizes is estimated.
The figure that the density (impurity concentration) of hot alms giver in each position of the crystallization that [Figure 13] forms for crystal pulling forms to doped with hydrogen crystallization and non-impurity-doped crystal pulling describes.
Symbol description
1 crucible
The 1a quartz crucible
The 1b black-fead crucible
2 heaters
3 raw material liquations
4 crystal pulling axles
5 seed chucks
6 monocrystalline
7 heat shielding bodies
Embodiment
Hereinafter an execution mode that the present invention relates to is described based on accompanying drawing.
Fig. 8 is the longitudinal section that is suitable for implementing the CZ stove of the silicon single crystal manufacture method in the present embodiment.
At first the structure to the CZ stove describes.
The CZ stove as shown in Figure 8, has the heater 2 of crucible 1 that is disposed at the central part in the chamber and the outside that is disposed at crucible 1.The black-fead crucible 1b that crucible 1 has with the outside remains on the double-decker that the inboard holds the quartz crucible 1a of melted silicon 3, drives rotation and lifting by the back shaft that is called as pedestal.Above crucible 1, be provided with the heat shielding body 7 of drum.Heat shielding body 7 has with graphite to be made shell, fills the structure of graphite felt in inside.The inner face of heat shielding body 7 forms the conical surface that internal diameter reduces gradually from the upper end to the bottom.The outer surface of upper of heat shielding body 7 is the conical surface corresponding to inner surface, and lower external face roughly forms to be faced directly so that the thickness of heat shielding body 7 increases gradually towards the below.
This CZ stove, the aimed dia of for example can growing are that 210mm, stem length (ボ デ ィ Long) for example are the monocrystalline of the 200mm of 1200mm.By heat shielding body 7, form the temperature gradient Gc of nucleus of crystal portion and the thermal field structure that temperature gradient Ge equates or the former is bigger of crystallization peripheral part.
At this moment, the specification example of heat shielding body 7 is as described below.The external diameter that enters crucible part for example for 470mm, minimum diameter S bottom for example for 270mm, radius to width W for example for example be 21 ° with respect to the slope θ of vertical direction for the inner surface of 100mm, inverted cone trapezoidal faces.In addition, the internal diameter of crucible 1 for example is that the height H of the following end distance molten surface of 550mm, heat shielding body 7 for example is 60mm.
When using the single-crystal growing apparatus of above-mentioned cross section structure to carry out crystal pulling, from the axial-temperature gradient of fusing point to 1370 ℃: monocrystalline central part (Gc) is that 3.0～3.2 ℃/mm, periphery (Ge) are that 2.3～2.5 ℃/mm, Gc/Ge are about 1.3.Even this state changes pulling rate and also changes hardly.
Then the establishing method to the operating condition that is used for growing silicon single crystal describes.
At first, in order to grasp hydrogen concentration and the permissible range that obtains the pulling rate of zero defect crystallization, making hydrogen concentration for example is the blending ratio of 0,0.1,3,5,8,10 volume %, for example monocrystalline of 210mm of aimed dia of growing under each condition.
That is, with the polycrystalline of high purity silicon for example 130Kg pack in the crucible, add p type (B, Al, Ga etc.) or n type (P, As, Sb etc.) dopant so that the resistivity of monocrystalline is for example 10 Ω m of desired value.Make in the device for ar gas environment and be decompressed to 1.33～13.3kPa (100～100torr), set and make hydrogen being that afore mentioned rules blending ratio below the 10 volume % flows in the stove with respect to argon gas.
Then, make the silicon fusion, make liquation 3 by heater 2 heating.Then, the crystal seed that is installed on seed chuck 5 be impregnated in the liquation 3, carry out crystal pulling in the time of crucible rotating 1 and crystal pulling axle 4.Crystal orientation be 100}, 111} or any one among the 110}, in order to make the crystallization dislocation-free crystal seed carried out necking down after, form shoulder, shouldering grows into the crystallization in target trunk footpath.
When the crystallization torso length for example reaches 300mm, make pulling rate fully greater than critical speed, for example be adjusted into 1.0mm/min, then, roughly reduce pulling rate point-blank, when torso length for example reaches 600mm according to crystal pulling length, make pulling rate for example be 0.3mm/min less than critical speed, with this pulling rate for example trunk of 1200mm of growing, after under usual conditions, finishing up, finish crystalline growth then.
The monocrystalline that to grow under different hydrogen concentrations is made and is contained near the tabular test film of crystal pulling axle along the rip cutting of crystal pulling axle, observes for the distribution to primary defective, carries out Cu decoration (デ コ レ one シ ヨ Application).At first, impregnated in each test film in the copper sulfate solution after, air dry, in nitrogen environment in 900 ℃ of heat treatments of implementing down about 20 minutes.Then, in order to remove the Cu silicide layer on test film top layer, impregnated in HF/HNO 3In the mixed solution, the tens of microns in top layer are removed in corrosion.By X ray topological approach (X Line ト Port グ ラ Off method) position of OSF ring or the distribution of each defect area are checked then.In addition, for example the density of the COP of this section is checked, for example with the Secco etch density of dislocation group checked with the OPP method.
So, use the defect distribution of the crystallization of the monocrystalline crystal pulling apparatus growth of satisfying Gc/Ge 〉=1, as shown in Figure 3, ring-type OSF produces the state of U word.If the increase hydrogen concentration then forms flawless position and enlarges as B '-C ' of Fig. 4, the scope (margin) that forms the pulling rate of zero defect crystallization enlarges.
In other words, shown in E '-C ' of Fig. 4, in the zone (PV zone) by the primary defective of no cavity type is that oxygen is separated out in the monocrystalline of the no primary defective that the zone (PI zone) that promotes the zone and do not have the primary defective of silicon type between lattice constitutes, in the present embodiment, be used for silicon dominant area pulling rate expanded range between the lattice of no primary defective monocrystalline that crystal pulling becomes only to contain the PI zone shown in the F ' of Fig. 4-C '.Specifically, compare with the situation of as shown in Figure 7 no hydrogen, the expanded range in PI zone is more than 4 times.
By above-mentioned crystal pulling experiment, obtain COP zone, OSF ring zone, V-type does not have primary defect area (PV zone) and the I type does not have primary defect area (PI zone), dislocation is rolled into a ball the V/G of each defect area such as zone and the relation (Fig. 9) of hydrogen concentration.
In addition, implement number place to 800mm and 700mm to the different parts of 1000mm by making the position that changes pulling rate arrive 600mm, 500mm, try to achieve the pulling rate scope (margin) of the no primary defectiveization of realization and the relation (Figure 10) of crystallization axial location at 300mm.By this Figure 10, can set the operating condition that is used to obtain not having primary defective monocrystalline.
In the present embodiment, in the inert environments gas of the gas of the material that contains hydrogen atoms during growing silicon single crystal, do not limit whether applying magnetic field to liquation by Czochralski method.Also can adopt the MCZ method that applies magnetic field.
So, by in the inert environments gas of the gas of the material that contains hydrogen atoms, silicon single crystal being carried out crystal pulling, can with can crystal pulling become expanded range to 4 times that crystallization does not radially contain the PI zone pulling rate of the monocrystalline of silicon dominant area (PI zone) between COP and dislocation group, lattice on the Zone Full with on carry out crystal pulling.Therefore, can make the monocrystalline vertical tube part all is silicon dominant area between lattice (PI zone).In the past, when so-called no primary defective monocrystalline is carried out crystal pulling, PI zone pulling rate must be set in the extremely narrow scope.By enlarging the PI zone velocity, can be extremely easily and with faster than in the past the no primary defective monocrystalline of pulling rate growth.
Then, the manufacture method to various wafers describes.
By setting the crystallization position corresponding to pulling rate, the crystallization of the no primary defective of can in the Zone Full from the top to the bottom, growing in the velocity interval shown in the solid line in Figure 10.
And by doped with hydrogen, the scope (margin) of not having a pulling rate of primary defective significantly enlarges shown in solid line from the scope of the dotted line that do not add hydrogen in the past as shown in figure 10, and the manufacturing yield that does not have primary defective crystallization greatly increases.
In addition, more than the higher limit shown in the solid line of Figure 10, pulling rate is set in about 1.7 times of higher limit during with interior speed, though can there be primary defective fully, the COP that is contained that can grow is of a size of the following crystallization of 0.1 μ m.If use this crystallization,, can make the top layer near zone of the above degree of depth of at least 1 μ m not have primary defective then by the annealing in environmental gas such as hydrogen or argon.And, be of a size of below the 0.1 μ m in order to make defective, can eliminate COP fully the zone by the degree of depth of the annealing about 1110 ℃/2hr about from the top layer to 1 μ m.
So, obtain containing the silicon single crystal bar of the hydrogen of desired concn and oxygen by the CZ method after, use shearing devices such as ID saw or fret saw to cut into slices according to common processing method to it after, be processed into the silicon single crystal wafer through steps such as chamfering, grinding, etching, polishings.And, except these steps, also there are various steps such as washing, can suitably change step according to purposes such as the change of sequence of steps, omissions.
In the manufacture method of the silicon wafer of present embodiment, the heat treatment as hot alms giver comprises: in non-oxidizing atmosphere gas in elevated temperature heat treatment steps such as 1000 ℃～1300 ℃ hydrogen annealings that carry out, argon annealing; The Low Temperature Heat Treatment step of carrying out under the state that has sufficient hot alms giver before the alms giver eliminates processing, described alms giver eliminates and handles is that alms giver in that being used to of carrying out before the above-mentioned high-temperature heat treatment suppresses about 650 ℃ * 1hr of resistivity change eliminates processing.
This Low Temperature Heat Treatment step is to be 0.2 ℃/min～2.0 ℃/min and to be undertaken by gradient heat treatment at 400 ℃～650 ℃ temperature, heating rate.In addition, in the Low Temperature Heat Treatment step, more preferably temperature range is that 500 ℃～600 ℃ and/or heating rate are 0.3 ℃/min～1.0 ℃/min.Carry out this Low Temperature Heat Treatment step so that the difference in oxygen concentration between before and after the above-mentioned high temperature heat treatment step is 1.5 * 10 17Individual atom/cm 3More than oxygen precipitate density after (ASTM-F1211979) and the above-mentioned high-temperature heat treatment be 1.0 * 10 10Individual/cm 3More than.
Figure 11 describes the board-like gradient thermal treatment device that is used to carry out the Low Temperature Heat Treatment step.
In the above-mentioned annealing device, as shown in the figure, have circular pedestal 11 that can mounting silicon wafer W and hold the reative cell 12 of said base 11 in inside.And, in the exterior arrangement of reative cell 12 pair halogen lamp that silicon wafer W heats 13 is arranged.
Pedestal 11 is formed by silicon carbide etc., the interior all side section of being provided with 11a of portion, on the above-mentioned section 11a of portion the circumference of mounting silicon wafer W.Be provided with supply port 12a and the outlet 12b that discharges the environmental gas G that is supplied with in the reative cell 12 to the surperficial supply environment gas G of silicon wafer W.In addition, the supply source 14 of supply port 12a and environmental gas G is connected.
When silicon wafer W being carried out Low Temperature Heat Treatment by this annealing device, behind mounting silicon wafer W on the pedestal 11, from the surperficial supply environment gas G of supply port 12a, under this state to silicon wafer W, light lamp 13, heat-treat with temperature conditions, the programming rate of above-mentioned scope.By this heat treatment, in silicon wafer W, form oxygen and separate out nuclear.
In containing the inert environments gas of gas that hydrogen atoms obtains material,, in this monocrystalline, under the state of growth, in the body piece, form highdensity hot alms giver (TD) thus by CZ method growing silicon single crystal.Obtain wafer by this single-crystal wafer, this wafer is implemented above-mentioned Low Temperature Heat Treatment step, in the body piece, form highdensity undersized oxygen thus and separate out nuclear, separate out nuclear, be suppressed at the slippage expansion that produces in the high-temperature heat treatment by the highdensity oxygen of this small size.
In the above-mentioned Low Temperature Heat Treatment step, handle, can in the body piece, form slippage in the inhibition high temperature heat treatment step and expand necessary highdensity undersized oxygen and separate out nuclear because the hydrogen doping wafer that contains highdensity hot alms giver is implemented low temperature gradients.
Wherein, in order to suppress the slippage expansion in the high temperature heat treatment step, under the temperature (more than 900 ℃) of the beginning expansion of staggering on the throne, it is important whether separating out the oxygen precipitate on the dislocation line of slippage propagation direction.Therefore, in the Low Temperature Heat Treatment step, if temperature range is set to the temperature that is higher than the said temperature scope, then might expand owing to slippage in high temperature heat treatment step and not preferred, the temperature that is lower than the said temperature scope is then not preferred owing to might be able to not promote essential oxygen to separate out karyomorphism one-tenth as if being set in.
As high-temperature heat treatment, except the hydrogen annealing that undertaken by DZ-IZ, argon annealing, can also enumerate the SIMOX annealing under the high temperature more than 1300 ℃, implemented etc.
In addition, can adopt the heat treatment that to handle with the RTA (RapidThermal Annealing) that heating and cooling are rapidly carried out in msec instruction or be undertaken by laser radiation.
In the present embodiment, by in the inert environments gas of the gas of the material that contains hydrogen atoms, silicon single crystal being carried out crystal pulling, the silicon wafer that fully has hot alms giver is implemented above-mentioned low temperature gradients heat treatment, can in wafer, be formed on the back residual SiO that can prevent the slippage expansion such as argon annealing 4
This wafer can directly be used for device manufacturing as common PW (polishing back wafer, minute surface wafer), also can be used as the substrate that SOI uses.
Wherein, the result that the V word crystal pulling of being undertaken by the silicon single crystal crystal pulling apparatus is estimated is described.
Change pulling rate to form the ratio O.7 → O.35 → O.7 of maximum pulling rate, at this moment, hydrogen concentration and furnace pressure during crystal pulling is respectively (a) O%, 30torr (b) 6%, 30torr (c) 6%, 70torr, carries out crystal pulling respectively, to crystal axis to the surface observe.
Result that following processing observes is implemented shown in Figure 12 A, B, C in the cut-out of above-mentioned crystallization surface.
So, the monocrystalline that will grow under different hydrogen concentrations is made and is contained near the tabular test film of crystal pulling axle along the rip cutting of crystal pulling axle, observes for the distribution to primary defective, carries out the Cu decoration.At first, impregnated in each test film in the copper sulfate solution after, air dry, in nitrogen environment gas in 900 ℃ of heat treatments of implementing down about 20 minutes.Then, in order to remove the Cu silicide layer on test film top layer, impregnated in HF/HNO 3In the mixed solution, corrosion is checked the position of OSF ring or the distribution of each defect area by the X ray topological approach after removing the tens of microns in top layer.
In addition, each zone and the pulling rate corresponding to Fig. 9 of this moment have the result of which kind of degree change shown in Fig. 7 and table 1 because of adding hydrogen.Pulling rate scope in each defect area of table 1 is measured by the width of observed each defect area that the crystal axis in nucleus of crystal portion is made progress and to be calculated.
Table 1
Figure C20058005022900221
By the result shown in Fig. 7 and the table 1 as can be known, by adding hydrogen, though the pulling rate scope in PV zone and ring OSF zone does not significantly change, but the pulling rate scope in PI zone, be to compare with the situation of not adding hydrogen under the situation of 30torr at furnace pressure, enlarge about 4.4 times, enlarge about 7 times under the situation of this external 70torr.Hence one can see that, depends on the hydrogen dividing potential drop, and the width in PI zone significantly enlarges.
Embodiment
Hereinafter the embodiment that the present invention relates to is described.
[embodiment 1]
In order to investigate the anti-slip characteristic in the high-temperature heat treatment, constant at pulling rate is that crystal pulling obtains silicon single crystal under the condition of 6% environmental gas for 0.7mm/min, hydrogen concentration, for the silicon wafer that obtains by this silicon single crystal section, implement 3 kinds of heat treatment steps shown in the table 2, the XRT (X-ray Topograph) that implements these silicon wafers estimates, the slip length of relatively hindering from the wafer support combustion boat based on resulting photo.The heat treatment step dependence result of die strength is as shown in table 2.
And heat treatment environment gas is all implemented under the Ar environmental gas.
[table 2]
Level Heat treatment The slip length ratio
1 The DK processing (650 ℃ * 30min) → annealing (1200 ℃ * 1hr) 1
2 Gradient heat treatment 1 → DK processing (650 ℃ * 30min) → annealing (1200 ℃ * 1hr) 0.5
3 Gradient heat treatment 2 → DK processing (650 ℃ * 30min) → annealing (1200 ℃ * 1hr) ＜0.1
" gradient heat treatment 1 " shown in the table 2 is to be the heat treatment of 2.5 ℃/min from 500 ℃～650 ℃ gradient speed, and " gradient heat treatment 2 " is to be the heat treatment of 0.3 ℃/min from 500 ℃～650 ℃ gradient speed.
By implementing " gradient heat treatment 2 ", distinguish that the slippage of hindering from combustion boat is inhibited basically.
Further, to the wafer behind the high annealing (level 1～3) in oxygen atmosphere gas, implement 1000 ℃ * 16hr append heat treatment after, with etch processes BMD is come to the surface, result that enforcement is counted to the BMD number and the difference in oxygen concentration between (Δ Oi) before and after the heat treatment are shown in table 3 with the bmd density/Δ Oi dependence of die strength.
[table 3]
Level Bmd density (/cm 3) Δ Oi (individual atom/cm 3)
1 1.0×10 9 1.0×10 17
2 5.0×10 9 1.3×10 17
3 1.5×10 10 1.5×10 17
Confirm by The above results, in order to suppress the slippage in the heat treatment, at least 1.0 * 10 10Individual/cm 3Above bmd density and the Δ Oi before and after the heat treatment are 1.5 * 10 17Individual atom/cm 3More than be necessary.
In addition, constant at pulling rate is the hydrogen doping crystallization that crystal pulling obtains total length 800mm under the condition of 6% environmental gas for 0.7mm/min, hydrogen concentration, cuts out wafer by this crystallization, by four probe method the ratio resistance at each position is measured.Then, after the heat treatment of 650 ℃ * 30min of enforcement is handled as the DK (donor killer) that eliminates hot alms giver, measure the ratio resistance of wafer once more.
Note has the impurity concentration (hot alms giver's density) by the variation conversion of the ratio resistance value before and after the processing of the DK in each position among Figure 13.Also note has the impurity concentration when not supplying with hydrogen as REF (non-impurity-doped).
By the result of figure as can be known, by adding hydrogen, can increase impurity concentration (hot alms giver's density).Thus, as shown in table 2, by Low Temperature Heat Treatment, can suppress the slippage expansion in the 1200 ℃ * 1hr annealing.
[embodiment 2]
Then, in order to investigate the anti-slip characteristic of realizing by the hydrogen concentration in the inert environments gas (volume %), make pulling rate be constant at 0.7mm/min, with 0.1%, 3%, 6%, 10%, 20%, 0% totally 6 levels change hydrogen concentration (volume %) growing silicon single crystal ingot in the inert environments gas, prepare the silicon wafer that cuts out by above-mentioned ingot.After implementing to be the low temperature gradients heat treatment of 0.3 ℃/min from 500 ℃ to 650 ℃ gradient speed for each silicon wafer, the DK that implements 650 ℃ * 30min handles and the high-temperature heat treatment of 1200 ℃ * 1hr.The XRT (X-ray Topograph) that implements these silicon wafers estimates, and is relatively longer from the slippage that the wafer support combustion boat is hindered based on resulting photo.Its result is as shown in table 4.And, all be to implement under the Ar environmental gas at heat treatment environment gas.
[table 4]
Level Hydrogen concentration (volume %) The slip length ratio
1 (example of the present invention) 0.1 1
2 (examples of the present invention) 3 0.5
3 (examples of the present invention) 6 ＜0.1
4 (examples of the present invention) 10 ＜0.1
5 (examples of the present invention) 20 ＜0.1
6 (comparative examples) 0 10
As shown in Table 4, the silicon wafer of example of the present invention (level 1～5) is compared with the silicon wafer of comparative example (level 6), can greatly suppress the slippage expansion.Particularly if the hydrogen concentration in the inert environments gas is then can be suppressed to more than 3% to detect the slippage expansion on visual level.
Industrial applicibility
According to the present invention, by growing silicon single crystal ingot in the inert environments gas of the gas of the material that contains hydrogen atoms, can obtain under the state of growth, containing highdensity hot alms giver's silicon single crystal. Cut out wafer by this crystallization, by implementing Low Temperature Heat Treatment, can form highdensity little oxygen precipitate, when carrying out high-temperature heat treatment more than 1000 ℃ with DZ-IG method etc., suppress slippage by precipitate to expand, prevent thus the reduction of intensity. By the present invention, can obtain having DZ layer integral in device forms and the silicon wafer of excellent strength.
In the silicon wafer of the present invention, can obtain only containing silicon dominant area between lattice in the wafer Zone Full, the density of oxygen precipitate and size and DZ width be remarkable uniform excellent wafer in the face of wafer.
In addition, according to the present invention, add hydrogen by combination in without the growth of grown-in defects crystallization, realize the pulling rate expanded range of zero defect, the zero defect crystallization of can stably growing significantly improves the manufacturing yield without the grown-in defects crystallization.

Claims (7)

1. the manufacture method of a silicon wafer, it is the manufacture method of silicon single crystal wafer, this method comprises:
In the inert environments gas of the gas of the material that contains hydrogen atoms, by the step of CZ method growing silicon single crystal,
Cut out the step of wafer by described silicon single crystal,
In non-oxidizing atmosphere gas, under 1000 ℃～1300 ℃, described wafer is implemented heat treated high temperature heat treatment step,
Before described high temperature heat treatment step, be lower than under the temperature of this heat treatment temperature, described wafer is implemented heat treated Low Temperature Heat Treatment step;
Hydrogen concentration in the described inert environments gas is under the condition of 1.3～13.3kPa at furnace pressure, is set in 0.1%～20% scope.
2. the manufacture method of silicon wafer according to claim 1 is characterized in that:
Also had before described high temperature heat treatment step, described wafer is implemented to be used to prevent that the elimination alms giver's of resistivity change heat treated alms giver from eliminating heat treatment step, described Low Temperature Heat Treatment step is before described alms giver eliminates heat treatment step, being lower than under the temperature that this alms giver eliminates heat treatment temperature, described wafer is implemented heat treated step.
3. the manufacture method of silicon wafer as claimed in claim 1 or 2, wherein, the temperature range of described Low Temperature Heat Treatment step is that 400 ℃～650 ℃, heating rate are 0.2 ℃/min～2.0 ℃/min.
4. the manufacture method of silicon wafer as claimed in claim 3, wherein, described heat treatment step is undertaken by gradient heat treatment.
5. the manufacture method of silicon wafer as claimed in claim 1 wherein, by described Low Temperature Heat Treatment step, makes the difference in oxygen concentration between of described high temperature heat treatment step front and back be determined as 1.5 * 10 according to ASTM-F121 1979 17Individual atom/cm 3More than.
6. the manufacture method of silicon wafer as claimed in claim 1 or 2, wherein, making the oxygen precipitate density after the described high-temperature heat treatment is 1.0 * 10 10Individual/cm 3More than.
7. silicon wafer, it is made by claim 1 or 2 described manufacture methods, and its oxygen precipitate density is 1.0 * 10 10Individual/cm 3More than.
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